Treatment of hydrocarbon oils



Patented Oct. 13, 1936 PATENT OFFICE 2,057,629 TREATMENT or HYDROCARBONOILS Jacque O. Morrell and Gustav Egloif, Chicago,

111., assignors, by mesne assignments, to Universal Oil ProductsCompany, Chicago, 111., a corporation of Delaware No Drawing.Application January 26, 1931, Serial No. 511,123. Renewed March 18, 19359 Claims. (01. 196-39) This invention relates to the treatment ofhydrocarbon oils, and refers more particularly to the refining ofrelatively low boiling hydrocarbon distillates at elevated temperatures,especially 1 5 those resulting from the conversion of relatively highboiling hydrocarbons at elevated temperatures.

In a specific embodiment the invention comprises subjecting hydrocarbon'oils to treatment with hydrochloric acid in the presence of a metallicoxide. More specifically, the invention comprises subjecting thehydrocarbon oils to treatment in the liquid phase in the presence of ametallic oxide and hydrochloric acid. Among 15 the metallic oxides whichmay be employed, and

as examples thereof may be mentioned: The oxides of calcium, magnesium,aluminum, zinc, tin, iron-copper, lead, mercury, cobalt, nickel,chromium, manganese, molybdenum, vanadium, tungsten, and the like.Mixtures of the oxides may also be employed.

In applying the process of the invention to practice a metallic oxide,preferably in a finely divided state, is added to the hydrocarbondistil- 25 late to be treated in association with hydrochloric acid. Thehydrochloric acid is prefaably added continuously to the hydrocarbonliquid while undergoing treatment. The hydrocarbon liquid may berefluxed in the presence of 30 the treating reagents or may be subjectedto distillation during the process of treatment. It is not essentialthat all of the hydrocarbon be in the liquid phase during treatment, butit is preferred that it be substantially in the liquid phase. 35 It isusual in the process that excess hydrogen chloride will be contactedwith the hydrocarbon vapors and may be removed either before, during orafter condensation. An alkaline material or solution of an alkalinematerial may be em- 40 ployed for the removal of the excess hydrogenchloride. Examples of such alkaline materials are solutions of caustic,soda, ammonia, and the like. The process has shown marked economies overthe ordinary methods of treatment such as 45 the use of sulphuric acidand alkaline solutions in various combinations.

As an illustration of the application of the process, the distillate tobe treated may contain some of the metallic oxide in suspension and may50 be fed continuously into a still maintained at a temperature suitablefor the vaporization of the desired product; for example, gasoline.Hydrochloric acid may be fed continuously into the body of the liquid,which is subjected to a rate 55 of distillation so that it issimultaneously subjected to the necessary time of treatment with thehydrochloric acid and the metallic oxide.

The temperatures employed will depend upon many factors, such aspressure, necessary time of treatment, properties of the distillate tobe treated, and others. Temperatures of from 200-275 F. have been foundsuitable for the treatment at atmospheric pressure, although lower andhigher temperatures have been employed with satisfactory results. At thehigher temperatures superatmospheric pressure may be employed, theprimary object being to maintain the oil undergoing treatmentsubstantially in the liquid phase. In many cases it is unnecessary totreat the lower boiling portions of the oil 5 undergoing treatment, andthis portion may be vaporized rapidly before the treatment becomeseffective; for example, in the treatment of a Pennsylvania orMid-Continent distillate from -40%, more or less, may be distilled ofibefore the treatment has become effective. In cases of this kind thetreating reagents may be added at the beginning of the operation, orafter a portion of the distillate has been removed.

As examples of the results which may be obtained by the application ofthe invention the following may be cited: A Mid-Continent crackeddistillate containing approximately 375 mgs. of gum per 100 005. and ofa dark yellow color when treated with zinc oxide in the presence ofapproximately one pound per barrel of hydrogen chloride in the form of adilute solution will produce a product containing approximately mgs. ofgum per 100 ccs. and of a color from 25 to on the Saybolt colorimeterscale and with an appreciable reduction in the sulphur content. Thetemperature of treatment is approximately 250 F.

A California distillate showing a gum content of 650 mgs. per 100 00s.,a sulphur content of approximately 0.3% and of a dark reddish browncolor, may be treated, employing approximately one pound of zinc oxideper barrel of oil treated and approximately one pound of hydrochloricacid in the form of an aqueous solution, and Will produce a product of25-30 Saybolt color with a gum content of approximately 35 mgs. per 10000s., more or less, and a sulphur content of approximately 0.2%.

Similar results to those described for zinc oxide may be obtained withtin oxide.

When iron oxide or copper oxide are employed the time and temperature oftreatment may have to be extended, for example, with a temperature of275 F. under a slight superatmospheric pressure, employing approximatelyone pound per barrel of hydrogen chloride in the form of an aqueoussolution, products of satisfactory color, odor and stability areproduced, with an appreciable reduction in sulphur content. Additionalsteam to that produced by the vaporization of the water in thehydrochloric acid may be employed. Direct treatment with gaseoushydrogen chloride has also been employed with satisfactory results.

The above examples are illustrative of the process of the invention onlyand are not to be construed as limitations thereof.

The treatment herein described may constitute the sole refining actionon the oil, or it may constitute one step in a series of refining steps.It may be preceded by the-usual treatments with refining agents suchassulphuric acid, caustic soda, plumbite, filtering earth. or the like,and may be succeeded by any combination of the above refining agents,followed, if desired, by distillation.

We claim as our invention:

1. A step in a process of refining the gasolinecontaining productresulting from the cracking of hydrocarbon oil, which comprisessubjecting said product in liquid condition to treatment with addedhydrochloric acid and a solid reagent whose major portion consists of asimple metallic oxide or oxides while maintainingv said oil at anelevated temperature.

2. A step in a process of refining the gasolinecontaining productresulting from the cracking of hydrocarbon oil, which comprisessubjecting said product in liquid condition to treatment simultaneouslywith added hydrochloric acid and a solid reagent whose major portionconsists of a simple metallic oxide or oxides while maintaining said oilat an elevated temperature.

3. A process for refining cracked hydrocarbonv distillate of motor fuelboiling range which comand-continuously adding hydrochloric acid to thedistillate during the heating.

5. A process for refining light cracked hydrocarbon oil which comprisestreating the oil, at

' a temperature above its normal boiling point and under sufficientsuperatmospheric pressure to maintain the major portion thereof inliquid phase; with added hydrogen chloride in the presence of steam anda zinc oxide.

6. A step in the refining of cracked gasolinecontaining distillates,which comprises treating the distillate simultaneously with addedhydrorchloric acid and a solid reagent whose major portion consists of asimple metal oxide or oxides.

7. A step in'the refining of cracked gasolinecontaining distillates,which comprises treating the distillate simultaneously with addedhydrochloric acid and zinc oxide.

- 8. A process for refining cracked gasolinecontainingdistiilates whichcomprises treating the distillate at elevated temperature simultaneouslywith added hydrochloric acid and a solidreagent consisting essentiallyof a simple metal oxide or oxides.

9. A process for refining cracked gasolinecontaining distillates whichcomprises treating.

the distillate at elevated temperature simultaneously with addedhydrochloric acidand zinc oxide.

. 'JACQUE C. MORRELL.

GUSTAV EGLOFF.

